Chapter 5: STATES OF MATTER

5.1 Gas
5.2 Liquids
5.3 Solids
5.4 Phase Diagram
 5.1 GAS
STATES OF
a) Explain qualitatively the basic assumptions of the kinetic
molecular theory of gases for an ideal gas. MATTER 5.3 SOLIDS
b) Define gas laws: a) Explain the fixed-shape of a solid.
i. Boyle’s law b) Apply the kinetic concepts to explain the following
ii. Charles’s law process:
iii. Avogadro’s law i. Freezing (solidification)
c) Sketch and interpret the graphs of Boyle’s and Charles’s Laws ii. Melting (fusion)
d) Perform calculations involving gas laws and ideal gas iii. Sublimation
equation. iv. Deposition
e) Determine molar mass of a volatile liquid using ideal gas c) Differentiate between amorphous and crystalline
equation. solids.
f) Define and perform calculation using Dalton's Law. d) State the following types of crystalline solids with
g) Explain the ideal and non-ideal behaviours of gases in terms appropriate examples:
of intermolecular forces and molecular volume. (*Used van i. Metallic
der Waals equation to explain the non-ideal behaviour) ii. Ionic
h) Explain the conditions at which real gases approach the ideal iii. Molecular covalent
behaviour iv. Giant covalent

5.2 LIQUIDS
5.4 PHASE DIAGRAM
a) Relate the properties of liquid to intermolecular forces, molecular
arrangement and molecular motion in explaining shape, volume, a) Define phase, triple point and critical point.
surface tension, viscosity, compressibility and diffusion. b) Identify triple and critical point on the phase
b) Explain vaporization and condensation process based on kinetic diagram.
molecular theory and intermolecular forces. c) Sketch the phase diagram of H2O and CO2.
c) Define vapour pressure and boiling point. d) Compare the phase diagram of H2O with CO2 and
d) Explain boiling process. explain the anomalous behaviour of H2O.
e) Illustrate the relationship between: e) Describe the changes in phase with respect to:
i. Intermolecular forces and vapour pressure i. Temperature (at constant pressure)
ii. Vapour pressure and temperature ii. Pressure (at constant temperature)
5.1 Gas
 Learning Outcomes
At the end of this topic, you should be able to:

a) Explain qualitatively the basic assumptions of the kinetic molecular

theory of gases for an ideal gas.
b) Define gas laws:
i. Boyle’s law
ii. Charles’s law
iii. Avogadro’s law
c) Sketch and interpret the graphs of Boyle’s and Charles’s Laws
d) Perform calculations involving gas laws and ideal gas equation.
 Learning Outcomes
At the end of this topic, you should be able to:

e) Determine molar mass of a volatile liquid using ideal gas equation.

f) Define and perform calculation using Dalton's Law.
g) Explain the ideal and non-ideal behaviours of gases in terms of
intermolecular forces and molecular volume. (*Used van der Waals
equation to explain the non-ideal behaviour)
h) Explain the conditions at which real gases approach the ideal behaviour
Kinetic Molecular Theory of Gases
❑There are FIVE basic assumptions (postulates) of kinetic molecular theory
of gases for ideal gas:

Postulate 1
Gas particles are in constant and random motion
➢ They frequently collide with one another and with the walls of container
Postulate 2
The volume of gas particles is negligible
➢ This is due to the size of gas particles are much smaller than the
volume of container
Postulate 3
Intermolecular forces (attractive and repulsive force) between gas particles are
negligible

Postulate 4
Collisions between gas particles are elastic
➢ kinetic energies of particles before the the collisions are same as that
of after collisions
➢ total kinetic energy is constant

Postulate 5
The average kinetic energy of the gas particles is directly proportional to
the absolute temperature
Gas Laws
❑ The physical behavior of gas can be described by four variables:

1. Pressure (P)
Boyle’s law
2. Volume (V)
Charles’s law
3. Temperature (T)
Avogadro’s law
4. Amount
(number of moles) (n)
GAS PRESSURE is caused
by gas molecules colliding
with container’s walls
1) Boyle’s Law
• At CONSTANT TEMPERATURE, the volume occupied by a fixed amount of
gas is inversely proportional to the pressure of a gas
1
𝑉∝ (T and n fixed)
𝑃
So, 𝑃𝑉 = 𝑘 Where k is a constant

Hence, P1V1 = P2V2

P1 and V1 = initial pressure and volume of the gas

P2 and V2 = final pressure and volume of the gas
 Graphs based on Boyle’s Law

Graph of V versus P Graph of V versus 1/P

V V

Slope=k

1
P P
• When gas is kept at constant temperature, its pressure is inversely
proportional to the volume.

• A doubling of the pressure causes the volume of the gas to decrease to

one-half its original value.
Graph of PV versus V

PV

V or P

PV = constant
 HOW THE KINETIC MOLECULAR THEORY EXPLAINS
THE BOYLE’S LAW?

• Gas pressure is a measure of the number of collisions between gas

particles and the walls of container.

• The smaller the volume at constant n and T, the more crowded

together the particles are and the greater the collisions.

• Thus, pressure of the gas increases as the volume decreases

V , P
Example 1:
A sample of gas occupies 12.0 L under a pressure of 1.2 atm. What would its
volume be if the pressure were increased to 2.4 atm?

Solution: P1 = 1.2 atm , P2 = 2.4 atm

V1 = 12.0 L , V2 = ?

Using Boyle’s law: 𝑃1 𝑉1 = 𝑃2 𝑉2 n & T are constant

𝑃1 𝑉1
𝑉2 =
𝑃2
1.2 atm × 12.0 L
=
2.4 atm
𝑉2 = 𝟔. 𝟎 𝐋
Example 2:
A cylinder contains a gas at 5.25 atm pressure. When the gas allowed to
expand to a final volume of 12.5 L, the pressure drop to 1.85 atm. What was
the original volume of the gas?

Solution: P1 = 5.25 atm , P2 = 1.85 atm

V1 = ? , V2 = 12.5 L

Using Boyle’s law: 𝑃1 𝑉1 = 𝑃2 𝑉2 n & T are constant

𝑃2 𝑉2
𝑉1 =
𝑃1
1.85 atm × 12.5 L
=
5.25 atm
𝑉1 = 𝟒. 𝟒𝟎 𝐋
2) Charles’s Law
• At CONSTANT PRESSURE, the volume occupied by a fixed amount of gas
is directly proportional to its absolute temperature

𝑉∝𝑇 (P and n fixed)

So, 𝑉
=𝑘 Where k is a constant
𝑇

Hence,
𝑉1 𝑉2 T in Kelvin (K)!
=
𝑇1 𝑇2 T (K) = T (oC) + 273.15

V1 and T1 = initial volume and temperature of the gas

V2 and T2 = final volume and temperature of the gas
 Graphs based on Charles’s Law

Graph of V versus T(K) Graph of V versus T(oC)

V V
Absolute
zero

T(K) -273.15 T(oC)

 HOW THE KINETIC MOLECULAR THEORY EXPLAINS
THE CHARLES’S LAW?

• Temperature is a measure of the average kinetic energy of the gas

particles.

• The higher the temperature at constant n and P, the faster the particles
move and more space they need to move around in to avoid increasing
their collisions with the walls of the container.

• Thus, volume increases as temperature increases.

T , V
AT CONSTANT PRESSURE

Initial Final
Example 1:
A sample of carbon monoxide gas occupies 3.20 L at 125 oC. At what temperature
will the gas occupy a volume of 1.54 L if the pressure remains constant?

Solution: V1 = 3.20 L V2 = 1.54 L

T1 = (125 + 273.15) T2 = ?
= 398.15 K

Using Charles’s law: 𝑉1 𝑉2 n & P are constant

=
𝑇1 𝑇2
𝑇1 𝑉2
𝑇2 =
𝑉1
398.15 K × 1.54 L
=
3.20 L
𝑇2 = 𝟏𝟗𝟏. 𝟔𝟏 𝐊
Example 2:
An engineer pumps air at 0oC into a newly designed piston–cylinder assembly.
The volume measures 6.83 cm3. At what temperature (in K) would the
volume be 9.75 cm3?
Solution: V1 = 6.83 cm3 V2 = 9.75 cm3
T1 = (0 + 273.15) T2 = ?
= 273.15 K

Using Charles’s law: 𝑉1 𝑉2

= n & P are constant
𝑇1 𝑇2
𝑇1 𝑉2
𝑇2 =
𝑉1
273.15 K × 9.75 cm3
=
6.83 cm3
𝑇2 = 𝟑𝟖𝟗. 𝟗𝟑 𝐊
3) Avogadro’s Law
• At CONSTANT PRESSURE AND TEMPERATURE, the volume of a gas is
directly proportional to the amount (number of moles) of the gas
present
𝑉∝𝑛 (P and T fixed)

So, 𝑉
=𝑘 Where k is a constant
𝑛

Hence,
𝑉1 𝑉2
=
𝑛1 𝑛2
V1 and n1 = initial volume and moles of the gas
V2 and n2 = final volume and moles of the gas
Graphs based on Avogadro’s Law

Graph of V versus n

n
HOW THE KINETIC MOLECULAR THEORY EXPLAINS
THE AVOGADRO’S LAW?

• The more particles there are in the gas sample, the more volume the
particles need at constant P and T to avoid increasing their collisions
with the walls of the container.

• Thus, volume increases as amount (number of moles) of gas particles

increases.

n , V
Example 1:
Nitrogen and oxygen gases react to form ammonia gas in the reaction
N2(g) + 3H2(g) → 2NH3(g)
If 500 mL N2 at 1 atm and 25oC were available for reaction, what volume (in
L) of H2, at the temperature and pressure, is required for the reaction?
Solution: V1 = 500 mL V2 = ?
n1 = 1 mol n2 = 3 mol

Using Avogadro’s law:

𝑉1 𝑉2 T & P are constant
=
𝑛1 𝑛2
𝑉1 𝑛2
𝑉2 =
𝑛1
500 mL × 3 mol
=
1 mol
𝑉2 = 1500 mL

𝑉2 = 𝟏. 𝟓 𝐋

So, the volume of H2 required = 1.5 L

Solution (Alternative):
Using Avogadro’s law:

N2(g) + 3H2(g) → 2NH3(g)

1 mol 3 mol 2 mol

1L 3L 2L

500 mL 500 x 3 mL 500 x 2 mL

= 1500 mL = 3000 mL
= 1.5 L

So, the volume of H2 required = 1.5 L

Example 2:
Nitrogen monoxide (NO) combines with oxygen to form nitrogen dioxide.
2NO(g) + O2(g) → 2NO2(g)
If 1.0 L oxygen gas at 30.25 ⁰C and 0.975 atm is used and there is an excess of NO,
what volume (in L) of NO gas at the same temperature and pressure will be
converted to NO2?

Solution: According to Avogadro’s Law:

2NO(g) + O2(g) → 2NO2(g)

2 mol 1 mol 2 mol

2L 1L 2L

So, the volume of NO converted = 2 L

 Ideal Gas
❑ Hypothetical gas whose pressure–volume–temperature relationship
can be accounted by the ideal gas equation

❑ Also called perfect gas

❑ Ideal gas equation: PV = nRT

Although no ideal gas actually
exist, most simple gas such as N2,
O2, H2, and noble gas show nearly
ideal behavior at ordinary
temperature and pressure
Universal Gas Constant, R

PV = nRT

PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.08206 L • atm / (mol • K)

L • atm • mol–1 • K–1

• Values of R :

Value of R Unit
0.08206 L atm mol-1 K-1
J mol-1 K-1
8.314 m3 Pa mol-1 K-1
L kPa mol-1 K-1
62.36 L mmHg mol-1 K-1
• Units for pressure, volume, gas constant and temperature

Pressure, P Volume, V Gas constant, R Temperature, T

Pa @ N m-2 m3 8.314 J mol-1 K-1 K

atm L @ dm3 0.08206 L atm mol-1 K-1 K

• Units conversion:

Temperature T (K) = T (oC) + 273.15

Pressure 1 atm = 760 mmHg

= 760 torr

= 101325 Pa @ 101.325 kPa

= 101325 N m-2
Example 1:
What pressure, in atm, is exerted by 54.0 grams of Xe in a 1.0 L flask at 20 ⁰C.

Solution: Mass of Xe
Mole of Xe =
Molar mass of Xe
54.0 g
=
131.29 g/mol
= 0.4113 mol Xe

Using ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇

(20+273.15) K
𝑛𝑅𝑇
𝑃=
𝑉
0.4113 mol (0.08206 L atm mol−1 K −1 )(293.15 K)
=
1.0 L
𝑃 = 𝟗. 𝟖𝟗 𝐚𝐭𝐦
Example 2:
What is the volume of a gas balloon filled with 4.00 moles of He when the
atmospheric pressure is 748 torr and the temperature is 30oC?

Solution: 𝑃 = 748 torr ×

1 atm
760 torr
= 0.984 atm

Using ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇

(30+273.15) K
𝑛𝑅𝑇
𝑉=
𝑃
4.00 mol (0.08206 L atm mol−1 K −1 )(303.15 K)
=
0.984 atm
𝑉 = 𝟏𝟎𝟏. 𝟏 𝐋
Relationship of Ideal Gas Equation with Mass, Molar
Mass and Density of Gas
PV = nRT
n = P n = m
V RT M
m = P
MV RT

mRT ρRT
M = OR M = since ρ = m
PV P V
m : Mass of the gas in g
M : Molar mass of the gas (Unit: g/mol)
Example 1:
An organic chemist isolates from a petroleum sample a colorless liquid with
properties of cyclohexane (C6H12). He obtains the following data to
determine its molar mass (M):

Volume (V) of sample gas = 213 mL

Mass sample gas(m) = 0.582 g
T = 100.0oC P = 754 torr

Is the calculated molar mass consistent with the liquid being cyclohexane?
Solution: 1 atm
𝑃 = 754 torr × 𝑇 = (100 + 273.15) K 𝑉 = 0.213 L
760 torr
= 0.992 atm = 373.15 K

Using ideal gas equation:

𝑃𝑉 = 𝑛𝑅𝑇
𝑚𝑅𝑇
𝑀=
𝑃𝑉
0.582 g (0.08206 L atm mol−1 K −1 )(373.15 K)
=
0.992 atm (0.213 L)
𝑀 = 𝟖𝟒. 𝟒 𝐠/𝐦𝐨𝐥
Consistent with cyclohexane (C6H12)
Example 2:
A 1.27 g sample of an oxide of nitrogen,believed to be either NO or NO2,
occupies a volume of 1.07 L at 25oC and 737 mmHg. What oxide is it?

Solution: 𝑃 = 737 torr ×

1 atm
𝑇 = (25 + 273.15) K
760 torr
= 0.970 atm = 298.15 K

Using ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇

𝑚𝑅𝑇
𝑀=
𝑃𝑉
1.27 g (0.08206 L atm mol−1 K −1 )(298.15 K)
=
0.970 atm (1.07 L)
𝑀 = 𝟐𝟗. 𝟗 𝐠/𝐦𝐨𝐥
The oxide is NO
Dalton’s Law of Partial Pressure
❑ In a mixture of unreacting gases, the total pressure is the sum of the
partial pressure exerted by each gas in the mixture (at constant V and T)

PTotal = PA + PB + PC + ……..

Where,

PA = XA PTotal PB = XB PTotal

X = mole fraction
Partial Pressure
• Pressures exerted by individual gas components in the gas mixture

PN = 1 atm P = 2 atm PTotal = PN + PAr

2 Ar 2

= 3 atm
Example 1:
A gaseous mixture made from 6.00 g O2 and 9.00 g CH4 is placed in a 15.0 L
vessel at 0oC. What is the partial pressure of each gas, and what is the total
pressure in the vessel?
Solution:
OXYGEN GAS (O2): METHANE GAS (CH4):

Mass (g) Mass (g)

Mol = Mol =
Molar mass (g/mol) Molar mass (g/mol)

6.00 g 9.00 g
Mole of O2 = Mole of CH4 =
32.0 g/mol 16.0 g/mol

= 0.188 mol O2 = 0.563 mol CH4

Solution (continues):
Using ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇

OXYGEN GAS (O2): 𝑛𝑅𝑇

𝑃𝑂2 =
𝑉
0.188 mol (0.08206 L atm mol−1 K −1 )(273.15 K)
=
15.0 L
𝑃𝑂2 = 𝟎. 𝟐𝟖𝟏 𝐚𝐭𝐦

METHANE GAS (CH4): 𝑛𝑅𝑇

𝑃𝐶𝐻4 =
𝑉
0.563 mol (0.08206 L atm mol−1 K −1 )(273.15 K)
=
15.0 L
𝑃𝐶𝐻4 = 𝟎. 𝟖𝟒𝟏 𝐚𝐭𝐦
Solution (continues):
By using the Dalton’s Law of partial pressure:

PTotal = PO 2 + PCH
4

= 0.281 atm + 0.841 atm

PTotal = 1.122 atm
Example 2:
What is the total pressure exerted by a mixture of 2.00 g of H2 and 8.00 g of N2
at 273 K in a 10.0 L vessel.

Solution:
HYDROGEN GAS (H2): NITROGEN GAS (N2):

Mass (g) Mass (g)

Mol = Mol =
Molar mass (g/mol) Molar mass (g/mol)
2.00 g 8.00 g
Mole of H2 = Mole of N2 =
2.0 g/mol 28.0 g/mol

= 1.0 mol H2 = 0.286 mol N2

Solution (continues):
Using ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇

HYDROGEN GAS (H2): 𝑛𝑅𝑇

𝑃𝐻2 =
𝑉
1.0 mol (0.08206 L atm mol−1 K −1 )(273 K)
=
10.0 L
𝑃𝐻2 = 𝟐. 𝟐𝟒𝟎 𝐚𝐭𝐦

NITROGEN GAS (N2): 𝑛𝑅𝑇

𝑃𝑁2 =
𝑉
0.286 mol (0.08206 L atm mol−1 K −1 )(273 K)
=
10.0 L
𝑃𝑁2 = 𝟎. 𝟔𝟒𝟏 𝐚𝐭𝐦
Solution (continues):
By using the Dalton’s Law of partial pressure:

PTotal = PH 2 + PN
2

= 2.240 atm + 0.641 atm

PTotal = 2.881 atm
Example 3:
The vapour pressure of water in air at 28⁰C is 28.3 torr. Calculate the mole
fraction of water in a sample of air at 28⁰C and 1.03 atm.

Solution: Pair at 1 atm = 760 torr

So, Pair at 1.03 atm = (1.03 x 760 torr) = 783 torr

𝑃𝐻2𝑂
𝑋𝐻2 𝑂 =
𝑃𝑎𝑖𝑟

28.3 𝑡𝑜𝑟𝑟
=
783 𝑡𝑜𝑟𝑟

𝑋𝐻2𝑂 = 0.036
Water Displacement
• Dalton’s law of partial pressure is often used to determine the pressure of
gas collected by water displacement.

Patm = Pgas + Pwater

• Note that, water vapour pressure varies with temperature

Example 1:
H2 is collected by water displacement. The total gas pressure is 99 kPa and the
room temperature is 24⁰C. At the temperature, the vapour pressure of water is
2.98 kPa. What is the pressure of H2?

Solution: PTotal = PH2 + PH2O

99.2 kPa = PH2 + 2.98 kPa

PH2 = 96.2 kPa

Example 2:
O2 is collected by water displacement. The atmospheric pressure is 1 atm and
the room temperature is 25⁰C. What is the pressure of O2?

Solution: Ptotal = Pair = 1 atm = 760 torr Oxygen gas will be mixed
Pwater at 25 ⁰C = 28.3 torr with water vapour

PTotal = PO2 + PH2O

760 torr = PO2 + 28.3 torr

PO2 = 731.7 torr

 Does an ideal gas exist ?

Any gas that obeys the ideal gas equation and has the
IDEAL GAS → properties as outlined by the Kinetic Molecular Theory
Ideal and Non-Ideal Behaviours of Gases
Ideal gas Real gas
(Ideal behaviour) (Non-ideal behaviour)

❖ Volume of gas particles is ❖ Gas particles have a

negligible compared to the certain volume & do
volume of container. occupy some space.

❖ Intermolecular forces ❖ There is intermolecular

between gas particles are forces between gas
negligible. particles
Deviation of gas from Ideal Behavior
• Real gases DO NOT show ideal behaviour.

• The deviation is due to:

i) Gas particles occupy space, that is, they have volume.
ii) The existence of intermolecular forces between gas
particles .

• The deviation is more significant at:

1) high pressure
2) low temperature.
1) At High Pressure
➢ Volume of container decreases

➢ Gas particles are closer to each other and begin to occupy a space
portion in the container.

➢ Hence,
i. The volume of gas particles is significant.
ii. The intermolecular forces between molecules become significant.

At high pressures, the particles are much

closer together and the attractive forces
cannot be ignored
2) At Low Temperature

➢ The kinetic energy of the gas particles decrease.

➢ Hence,
i. The gas particles move at low speed
ii. The intermolecular forces between molecules become significant.
Plot of PV/RT versus the Pressure(P) of 1 mole of Various Gases at 273 K(0oC)

CH4
PV N2
H2
RT
NH3
Ideal gas
1.0

P / atm
5 atm

When P , Deviation from ideal behavior

Plot of PV/RT versus the Pressure(P) of 1 mole of N2 at Various Temperature

PV 293 K
RT 203 K

673 K

1000 K
1.0 Ideal gas

P / atm

When T and P , Deviation from ideal behavior

Van der Waals Equations

• Real gas obey Van der Waals equation.

• To describe real gas behavior at high pressure and low temperature
more accurately, the ideal gas equation need to be modified:

1) Adjust the measured PRESSURE UP

(to account for intermolecular force between gas molecules)

2) Adjust the measured VOLUME DOWN

(to account for the molecular volume)
 Pressure Volume correction
correction term term

n2a Where,
P + (V – nb) = nRT
V2 a, b are Van der Waals constants

1) Pressure correction term

• The pressure of a real gas is smaller than expected from the ideal gas
𝑛2 𝑎
equation, so, the factor 2 is added to the P term.
𝑉

2) Volume correction term

• The volume of a real gas is smaller than expected from the ideal gas equation, so,
the factor nb is subtracted from the V term
Example:
A 1.98 L vessel contains 215 g (4.89 mol) of dry ice. After standing at 26 ⁰C
(299 K), the CO2(s) changes to CO2(g).

Pideal gas law = 60.6 atm

Pvan der Waals = 45.9 atm

Preal = 44.8 atm

Pideal gas law is 35.3% greater than Preal, BUT

Pvan der Waals is only 2.5% greater than Preal
Preal < Pideal

• The attractive force between gas molecules slow down the movement of
molecules

• So, there is less collision between molecules and the wall

• Thus, pressure exerted by real gas is less compared to ideal gas

(ideal gas → no attraction at all → more pressure exerted on the wall)
Veffective < Vcontainer
• In the ideal gas equation, V represents the volume of the container.
V = Vcontainer
• However, each molecule in real gas occupy a finite volume.
• Therefore, volume occupied by gas molecules has to be taken into consideration.
• The volume occupied by gas molecules must be subtracted from the total volume
Veffective = Vcontainer - nb

Where,

Vcontainer Veffective n : moles of molecules

b: constant representing the
nb
volume occupied by the
molecules
• Value of a indicate how strongly molecules of gas attract each other.
➢ The stronger attraction of gas molecules, the higher a value.

Attractive force a

• Value of b indicate the molecular size of molecules gas .

➢ The larger the molecule (or atom), the higher b value.

Molecular size b
Van der Waals Constant

➢ Experimentally determined positive numbers used in the Van der Waals

equation to account for the molecular interactions and molecular
volume of real gases

➢ The values of a and b are specific for a given gas

➢ a relates to the number of e-, which in turn relates to the complexity of

a molecule and the strength of its molecular attractions

➢ b relates to molecular volume

➢ Van der Waals constants for some common gases:
 Pideal = Preal + n2a
V2
PV = nRT
Veffective = Vcontainer - nb

(Preal + n2a ) (V – nb) = nRT

V2
n = number of moles
a = constant related to the strength of IMF between molecules
b = constant representing the volume occupied by gas molecules

Known as the Van der Waals equation !

❑Even for a real gas at ordinary pressures, the molecules are very far apart:
• Attractive forces are miniscule
n2a
P +  P
V2

• Molecular volume is a miniscule fraction of the container volume

V – nb  V

At ordinary conditions, the Van der Waals equation

becomes the ideal gas equation
Conditions at Which Real Gases Approach the Ideal Behaviour

1) At Low Pressure (Constant Temperature)

• Volume of container is increased.
• The gas particles are far apart in a large volume
• The intermolecular forces are negligible
• Volume of gas molecule is too small compared to volume of container,
thus volume of gas molecules are negligible.
• Hence, it obey kinetic molecular theory
• Thus, the gas behave ideally
2) At High Temperature (Constant Volume)

• Gas particles have high kinetic energy and move at high speed
• Gas particles are able to overcome intermolecular forces that act
between them.
• The intermolecular forces are negligible
• Hence, it obey kinetic molecular theory
• Thus, the gas behave ideally.
5.2 Liquids
 Learning Outcomes
At the end of this topic, you should be able to:

a) Relate the properties of liquid to intermolecular forces, molecular

arrangement and molecular motion in explaining shape, volume, surface
tension, viscosity, compressibility and diffusion.
b) Explain vaporization and condensation process based on kinetic
molecular theory and intermolecular forces.
c) Define vapour pressure and boiling point.
d) Explain boiling process.
 Learning Outcomes
At the end of this topic, you should be able to:

e) Illustrate the relationship between:

i. Intermolecular forces and vapour pressure
ii. Vapour pressure and temperature
Properties of Liquid

Shape and
Diffusion volume

Properties
of liquid
Compressibility
Surface tension

Viscosity
1) Shape and Volume
Liquid has a definite volume but not a definite shape
• This is because particles arranged closely but not rigidly
• The particles are held together by intermolecular force, but they able
to move freely
• This causes liquid to have moderate fluidity and take the shape of
container
• Thus, liquid conforms to shape and volume of container
2) Surface Tension
• Surface tension is energy required to increase surface area by a unit area
• It is caused by the intermolecular attractive forces acting within the
liquid molecules
• Molecules at the surface are pulled inwards and sideways from the
neighboring molecules
• The inner pull on the surface molecules cause the liquid to minimize its
surface area.
• Hence, the stronger the intermolecular attractive force, the higher the
surface tension of a liquid.
 Surface tension is the
tendency of liquid
surface at rest to
shrink into minimum
surface area possible.
Surface tension is
what allows object with
higher density to float
on the liquid.
Intermolecular forces ↑
surface tension ↑
3) Viscosity
• Viscosity is the resistance/tendency of a liquid to flow
• The greater the viscosity, the harder/slower it flows.
• Factors affecting the viscosity of a liquid:
i. Size of molecules
ii. Intermolecular forces acting between molecules
iii. Temperature of the liquid
i. Size of molecules

➢ As the molar mass (bigger size) INCREASE, the resistance to flow INCREASE
(harder to flow).
➢ So, viscosity of liquid INCREASE.

ii. Strength of intermolecular attractive forces

➢ As the strength of IMF INCREASE, the resistance to flow INCREASE

(harder to flow).
➢ So, viscosity of liquid INCREASE.
iii. Temperature

➢ As the temperature INCREASE, the average kinetic energy of molecules

INCREASE.
➢ Molecules move FASTER and can overcome the intermolecular forces
more easily.
➢ The resistance to flow DECREASE (easier to flow).
➢ So, viscosity of liquid DECREASE.
• Hence, the viscosity of the liquid INCREASES if

Size of molecules INCREASES

Intermolecular forces of
INCREASES
molecules
Temperature DECREASES
4) Compressibility
Liquid are slightly compressible.

• In liquid, the particles are close together

• There is very little empty space between the molecules

• Hence, liquid is more difficult to compress than gas

5) Diffusion
Liquid diffuse slower than gas
• Diffusion is the movement of particles from a region of higher
concentration to a region of lower concentration.
• Diffusion rate of liquid is much slower than gases , but faster than solid.
• This is because:
➢ molecules of liquid are close together
➢ they have lower kinetic energy than gases
➢ stronger intermolecular forces restrict the movement of the
liquid molecules.
Vaporisation and Condensation

Vaporisation

LIQUID GAS

Condensation
 VAPORISATION
Definition: Process in which a liquid
is changed into a gas
When heated, the kinetic energy of
liquid molecules increases,
- molecules will move faster.
- more molecules possess sufficient
kinetic energy to overcome the
intermolecular forces
- The molecules escape from the
surface as vapour molecules.
CONDENSATION
Definition: Process in which a gas is
changed into a liquid
When cooled, the kinetic energy of
liquid molecules decreases,
- molecules will move slower.
- they do not have sufficient
kinetic energy to remain as
vapour molecules.
- Molecules come closer, attract
one another and return as
liquid molecules.
❑ Factors affecting rate of evaporation.
Surface area ↑, vaporization rate ↑
1) Surface area Number of molecules with high energy
escaping from surface increase

Temperature ↑, vaporization rate ↑

More molecules have higher kinetic energy
2) Temperature
Number of molecules escape from surface
increase.

3) Strength of IMF Strength of IMF ↓ , vaporization rate ↑

1) Vapour Pressure
• Is the pressure exerted by vapour in equilibrium with its liquid in a closed
container.
• Molecules escape from the surface of a liquid are referred to as vapour
molecules.

In an open system :
Vapour molecules which evaporate off will diffuse away.

In a closed system :
Vapour molecules which leaves the surface cannot escape from the
system.
• The vapour molecules remain in the container and in contact with the
surface of the liquid.

• These molecules are in constant random motion. C.ontinually strike:

- the wall of the container
- other vapour molecules
- the surface of the liquid molecules

• Every time the vapour molecules hit the wall of the container, pressure is
exerted.
Volatility of liquid

• Volatile liquids
➢ High vapour pressures at room temperature

• Non-volatile liquids
➢ Very low vapour pressures at room temperature
Example: Vapor pressure (torr)

• At any given temperature (example: 20oC), Diethyl ether

diethyl ether has the highest vapor

pressure and water the lowest
ethanol

• Diethyl ether has the weakest

intermolecular forces and water
water
the strongest

Temperature (oC)
Factors Affecting Vapour Pressure

Temperature ↑
- molecules move faster,
1) Temperature
- easy to escape to form vapour
molecules.
- vapour pressure is high

Weak intermolecular forces,

- liquid molecules easy to escape to form
2) Strength of IMF
vapour.
- Vapour pressure is high
2) Boiling Point
• The temperature at which the vapour pressure of a liquid is equal to the
external (atmospheric) pressure

• For example, the boiling point of water is:

100⁰C at 760 torr (sea level)

94 ⁰ C at 610 torr (Boulder, Colorado)

72 ⁰ C at 270 torr (Mt. Averest)

• Normal boiling point
➢ The temperature at which a liquid boils when the external pressure
is 1 atm
 KEEP IN MIND

If the pressure is not mentioned when the boiling point is

measured, we assume it as normal boiling point (at 1 atm) .
Factors Affecting Boiling Point

Atmospheric pressure ↓
- Less heat needed to make vapour
1) Atmospheric Pressure
pressure equals to atmospheric pressure
- Boiling point decrease

2) Strength of IMF Strength of IMF ↑ , boiling point ↑

 KEEP IN MIND

Strength of intermolecular forces depend on:

1) Types of forces
E.g. H bond is much stronger than van der Waals force

2) Molar mass
E.g.
Cl2 (molar mass = 70.91 g/mol) has a higher boiling point than
F2 (molar mass = 38.00 g/mol)
Size of atom / molecule ↑
Intermolecular forces ↑
Vapour pressure ↓
Boiling point ↑
 SUMMARY

weaker higher
Lower
attractive vapor
boiling point
force pressure
Example 1:
A beaker of water is placed in closed container. Predict the effect on the
vapor pressure of the water when
(a) its temperature is lowered
(b) the volume of container is double
(c) more water is added to the beaker
 Solution:
(a) its temperature is lowered
 decrease

(b) the volume of container is double

 no change

(c) more water is added to the beaker

 no change

The vapor pressure of a liquid is affected by temperature and intermolecular forces.

Example 2:
Which of the following statement is true?
(a) Liquid A boils at a lower temperature than liquid B. This fact
indicates that liquid A has weaker intermolecular forces than B.
(b) Liquid M boils at a higher temperature than liquid N. This indicates
that M has a higher vapor pressure than N at any temperature.
Solution:
a) Liquid A boils at a lower temperature than liquid B. This fact
indicates that liquid A has weaker intermolecular forces than B.
 true

b) Liquid M boils at a higher temperature than liquid N. This indicates

that M has a higher vapor pressure than N at any temperature.
 false
Example 3:
Explain the following statement:
(a) Liquid with long molecules has higher viscosity than that with
spherical ones.
(b) Liquid molecules with higher molar mass more viscous than
that of a lower molar mass
Solution:
a) Liquid with long molecules has higher viscosity that with spherical ones
 Long molecules has larger surface area, so it has stronger
intermolecular forces (Van der Waals).

b) Liquid molecules with higher molar mass more viscous than that of
a lower molar mass
 Molecules with higher molar mass has a larger size, means larger
surface area, so it has stronger intermolecular forces (Van der
Waals).
Example 4:
The vapor pressure curves for four substances are shown in the plot. Which
one of these four substances will have the greatest intermolecular
attractive forces at 25 ⁰C? Explain your answer.

A B
C D
Vapor pressure (atm)

0 25 50 75 Temperature (⁰C)
Solution:

ANS: D

The greater intermolecular force, the lower vapor pressure

(D is the least volatile)
Example 5:
By referring to the graph shown, what is the boiling point of water when
the external pressure is 187.5 mmHg?

Solution:

65 ⁰C
5.3 Solids
 Learning Outcomes
At the end of this topic, you should be able to:
a) Explain the fixed-shape of a solid.
b) Apply the kinetic concepts to explain the following process:
i. Freezing (solidification)
ii. Melting (fusion)
iii. Sublimation
iv. Deposition
c) Differentiate between amorphous and crystalline solids.
d) State the following types of crystalline solids with appropriate examples:
i. Metallic
ii. Ionic
iii. Molecular covalent
iv. Giant covalent
Properties of Solid

Shape and volume Motion of molecules

Maintain it own shape and size Vibrate about fixed positions

Compressibility Density Ability to flow

Almost none High Almost none
1) Why solid are in fixed-shape ??

• Atoms / molecules in solids are closely-packed together in

a definite order.

• They can only vibrate and rotate about fixed position.

• They have rigid arrangement & cannot move freely

2) Processes that solid undergo

Melting Sublimation

SOLID LIQUID SOLID GAS

Freezing Deposition
Melting (Fussion)
• Solid changes to liquid

• When solid heated, the particles gain kinetic

energy and vibrate faster H2O(s) → H2O(l)

• At certain temperature, the particles have enough kinetic

energy to break free of their fixed position

heated

solid liquid
Freezing (Solidification)
• Liquid changes to solid

• When liquid cooled, the particles lose kinetic

energy and move more slowly. H2O(l) → H2O(s)

• Intermolecular forces become stronger and particles

become fixed in position.

Cooled
(temperature decreased)

liquid solid
 Sublimation
• Solid changes directly to gas without becoming a liquid

• When a substance sublimes, molecules leave the CO2(s) → CO2(g)

surface of the solid, where they are held by less tightly (dry ice)
than the interior

• The combination of intermolecular attractions and atmospheric pressure

is not great enough to keep the particles near to one another when they
leave solid state.

heated

solid gas
 Deposition
• Gas changes directly to solid without becoming a liquid

When iodine vapor comes in

contact with a cold surface,
it deposits iodine crystals
I2(g) → I2(s)

At ordinary atmospheric
pressure, solid iodine
sublimes: I2(s) → I2(g) I2(g) → I2(s)
3) Types of Solid
• Solid can be divided into two types based the orderliness of their particles:
i. Crystalline solid
ii. Amorphous solid

Arrangement of particles in crystalline and

amorphous solid
• Difference between crystalline and amorphous solid.
Crystalline Solid
Shape Well-defined shape
Particles (atom, molecules
Arrangement of
or ions) are in orderly
Particles
arrangement
Examples metal, salt and diamond
Amorphous Solid
(Non-crystalline)
Poorly-defined shape
Lack in orderly
arrangement of their
particles
charcoal, rubber , glass
• There are 4 types of crystalline solid:

Metallic Solid Molecular Covalent Solid

Types of
Crystalline
Solid
Ionic Solid Giant Covalent Solid

• These crystalline solids are defined by the type of particles in the crystal
and the type of forces between the particles.
Metallic Solid
• Lattice points occupied by metal atoms

• Held together by strong metallic bond

• Soft to hard, low to very high melting point

• Good conductor of heat and electricity

• Malleable and ductile

• Example: Na, Zn, Fe

• Example : Magnesium metal

e– e– e–
e– e– e–
nucleus & Mg2+ Mg2+ Mg2+
inner shell e-
e– e– e–
e– e– e–
Mg2+ Mg2+ Mg2+

mobile “sea”
of e-
(valence e-)
Electron sea model
Ionic Solid
• Lattice points occupied by cations and anions

• Held together by strong electrostatic attraction

• Hard, brittle, high melting point

• Poor conductor of heat and electricity (in solid state) but does so in
molten state or in aqueous solution due to the free moving ions
Lattice points in an ionic solid

Cl- Na+

Example of ionic solid : NaCl

Molecular Covalent Solid
• Lattice points occupied by molecules

• Held together by intermolecular force

• Fairly soft, low to moderate melting point

• Poor conductor of heat and electricity

• Example: ➢ Nonpolar molecule : P4, S8

➢ Polar molecule : H2O (ice)

ICE
Giant Covalent Solid
• Also called network solid.

• Held together by strong covalent link and forms network

• Very hard, very high melting point

• Usually poor conductor of heat and electricity

• Example: ➢ C allotrope (diamond)

➢ SiO2
C allotrope Covalent bond
(diamond) SiO2

135
 Types of Crystalline Examples Intermolecular Forces/ bonding
Solids
1. Ionic solid NaCl, CaF2 Ionic bonding

2. Metallic solid All metals: Fe, Na, Mg Metallic bonding

3. Molecular covalent • All covalent Van der Waals forces

solid molecules Hydrogen bonds
• Simple molecules
• H2O
• O2
4. Giant covalent crystal • Diamond • Covalent bond
• Graphite • Van der Waals forces
• SiO2
5.4 Phase Diagram
 Learning Outcomes
At the end of this topic, you should be able to:
a) Define phase, triple point and critical point.
b) Identify triple and critical point on the phase diagram.
c) Sketch the phase diagram of H2O and CO2.
d) Compare the phase diagram of H2O with CO2 and explain the
anomalous behaviour of H2O.
e) Describe the changes in phase with respect to:
i. Temperature (at constant pressure)
ii. Pressure (at constant temperature)
 Phase
❑ A homogenous part of a system in contact with other parts of the system
but separated from by well-defined boundary

❑ Phase consist of :
• Solid gas
• Liquid
• Gas liquid

solid
Example :

two phases one phase

Solid phase : ice liquid

Liquid phase : water

two phase
liquid (but heterogeneous)

Oil + water
Example :

one phase
One gas gas
only

Mixture of one phase

gases gas
 System Phase Description
Gases are well mixed.
Mixture We cannot see the boundary
1
of gases between the gases.

Two liquids We can see the boundary between

Do not mix 2 the two liquids.
(oil-water)
Two liquids We cannot see the boundary of
well mixed 1 the solution.
(alcohol-water)
Phase Diagram
❑ A diagram showing the regions of pressure and temperature at
which a substance exists as a solid, liquid or vapor phases are
thermodynamically stable.
❑ It combines equilibrium curves of:
• liquid gas : Line OA
• solid liquid : Line OC
• solid gas : Line OB
 LINE • Represents the boundary between two phases.
• Two phases can exist together at equilibrium
AREA • Represents the conditions under which the
(REGION) substance will be in that particular phase

TRIPLE POINT • Where the three phases of solid, liquid and gas can
exist together at equilibrium
• This is where three lines meet together

CRITICAL • Gives the highest temperature at which the

POINT substance can exist in the liquid phase.
• Liquid-gas line ends
1) Triple Point
• Solid, liquid and vapor simultaneously exist in equilibrium
2) Critical Point
• The end of liquid–gas line

• The highest temperature at which a gas can be liquefied

• Density of liquid equal to density of gas

• Above the critical point, the liquid phase cannot exist, regardless the
pressure
➢ Phase boundaries disappears
➢ Separate liquid and gas phase no longer exist
• At this point, the average kinetic energy of the molecules is so high that
the vapor cannot be condensed no matter how much pressure is applied
3) Supercritical Region
• When a compound is subjected to a pressure and a temperature
higher than its critical point, the fluid is said to be supercritical.
• In the supercritical region, the fluid exhibit particular properties and
has an intermediate behaviour between that of liquid and a gas.
General Shape For A Phase Diagram
Pressure (atm)

Critical point: above this

B C point, the liquid & a gas
phases
become indistinguishable
LIQUID
SOLID Q R
P GAS
O Triple point: T & P at which the 3 phases exist in equilibrium

A
Temperature (K)
Example 1:
Predict the phase changes.
(a) A-B
(b) B-C
(c) C-D
(d) D-E
(e) E-F
(f) F-G
Solution:
(a) A-B

( gas ) → ( gas ⇌ solid ) → ( solid )

Solution (continues):
(b) B-C

( solid ) → ( solid ⇌ liquid ) → ( liquid )

Solution (continues):
(c) C-D

( liquid ) → ( liquid ⇌ gas ) → ( gas )

Solution (continues):
(d) D-E

( gas ) → ( gas ⇌ liquid ) → ( liquid )

Solution (continues):
(e) E-F

( liquid ) → ( liquid ⇌ solid ) → ( solid)

Solution (continues):
(f) F-G

( solid ) → ( solid ⇌ liquid ) → ( liquid )

Example 2:
6●

Pressure (atm)
●
A 5 ● 4
●
3
2
●
1 C
●

Temperature (oC)

(a) What phase is present in region A, region B and region C?

(b) What phases are in equilibrium at point 1, point 2, point 3 and point 5?
Solution: 6●

Pressure (atm)
●
A 5 ● 4
●
3
2
●
1 C
●

Temperature (oC)

(a) A: solid B: liquid C: gas (b) Point 1: solid and gas

Point 2: solid, liquid, and gas
Point 3: liquid and gas
Point 5: solid and liquid
Phase Diagram of CO2
• CO2 is a gas under normal conditions (25oC, 1 atm)

Pressure (atm)
O

-78oC -57oC
• LINE OA: CO2(s) CO2(g)

• Solid and gas exist in equilibrium

B

Pressure (atm)
O

-78oC -57oC
• LINE OB: CO2(s) CO2(l) (melting / freezing line)

• Solid and liquid exist in equilibrium

Pressure (atm)
O

-78oC -57oC
• LINE OC: CO2(l) CO2(g) (boiling curve)

• Liquid and gas exist in equilibrium

B

Pressure (atm)
O

-78oC -57oC
• POINT O : Triple Point ( –56.4oC, 5.2 atm)
• Solid, liquid and vapor exist in equilibrium

C
vapor

Pressure (atm)
liquid solid O

-78oC -57oC
 Above the critical point, the
• POINT C : Critical Point (31oC, 73 atm) liquid phase cannot exist,
regardless the pressure

Pressure (atm)
O

-78oC -57oC
• AT PRESSURE < 5.2 ATM:
• Phase change from solid → gas or vice versa
• When solid CO2 heated at 1 atm, it sublimes at –78oC
B

Pressure (atm)
O

-78oC -57oC
• AT PRESSURE > 5.2 ATM:
• Phase change from solid → liquid → gas or vice versa

Pressure (atm)
O

-78oC -57oC
• AT TEMPERATURE < –57OC:
• Phase change from gas → solid or vice versa
(low P) (high P)
B

Pressure (atm)
O

-78oC -57oC
• AT TEMPERATURE > –57OC:
• Phase change from gas → liquid → solid or vice versa
(low P) (high P)

Pressure (atm)
O

-78oC -57oC
• The phase diagram for CO2 is typical of most substances in
that solid–liquid line slopes to the right (positive slope)

• It means melting point (or freezing point) increase when the

pressure increase
 POSITIVE SLOPE
(Melting point increase when pressure increase)

Reason:
➢ Solid CO2 is more dense (occupy smaller volume) than liquid CO2.

➢ At high pressure, it favour the formation of solid CO2 which has

smaller volume.

➢ More heat is needed to melt the solid CO2.

➢ Solid CO2 melts at higher temperature at high pressure.

 Some
liquid
freeze
liquid liquid
liquid

P↑ solid solid
solid

• Pushing down the piston decrease the volume of both solid and
liquid by a small amount

• Pressure increases

• Some liquid freezes, producing the more dense solid

Phase Diagram of H2O
• H2O is a liquid under normal conditions (25oC, 1 atm)
• At 1 atm, phase change from solid → liquid → gas
or vice versa
• At 1 atm,
➢ melting point / freezing point = 0oC
➢ boiling point = 100oC
• POINT O = Triple Point ( 0.01oC, 0.006 atm)
• POINT C = Critical Point ( 374oC, 218 atm)
• The phase diagram for H2O is one of few substances in that
solid–liquid line slopes to the left (negative slope).

• It means melting point decrease when pressure increase.

Phase Diagram (CO2 vs H2O)

• The phase diagram for CO2 has a solid–liquid curve with a

positive slope, and the one for H2O has a solid–liquid line
with a negative slope.

• What macroscopic property can distinguish CO2 from H2O?

 CO2 H2O

If the solid is more dense than the liquid, the solid–liquid line
slopes to the right; if less dense, to the left.
Example:
Predict what would happen as a result of the following changes: (State the phase changes)
(a) Starting at A, we raise the temperature at constant pressure (isobaric heating).
(b) Stating at C, we lower, the temperature at constant pressure (isobaric cooling).
(c) Starting at B, we lower the pressure at constant temperature (isothermal depressurized).

P
B
A

C
T
Solution:
(a) - Raising the temperature at constant pressure beginning at A implies
starting with solid ice and warming until melting occurs.

- If the warming continued, the liquid water would eventually boil and
change to steam.

- Further warming would increase the temperature of the steam.

liquid
P solid
B
A

gas
C

T
Solution (continues):
(a) Phase changes:

(solid) → (solid ⇌ liquid) → (liquid) → (liquid ⇌ gas) → gas

Solution (continues):
(b) - At point C water is in the gas phase.

- Cooling without changing the pressure would eventually results in the

formation of solid ice.

- Liquid water would never form.

liquid
P solid
B
A

gas
C

T
Solution (continues):
(b) Phase changes: (gas) → (gas ⇌ solid) → (solid)
Solution (continues):
(c) - At B the water is the liquid phase.

- Lowering the pressure without changing the temperature would

eventually result in boiling and conversion of water to the gas phase.

liquid
P solid
B
A

gas
C

T
Solution (continues):
(c) Phase changes: (liquid) → (liquid ⇌ gas) → (gas)